Process for breaking petroleum emulsions



Patented Jan. 1935 i I msassa mzoorzssv ron BREAKING rErnoLEuM EMULSIONS Melvin Dc-Grootc, St. Louis, and Bernhard misci- Webster Groves, Mm, assiznors to Tretollte Company, Webster Groves, Mm, a corporation of Missouri- No Drawing. Application January 6, 1934 sci-n1 No. 705,616

This invention relates to the treatment of most important members, fatty acid sulfates and emulsions of mineral oil and water, such as fatty sulfonic acids, as described in Industrial petroleum emulsions, for the purpose of sep- 8: Engineering Chemistry, Analytical Edition, arating the oil from the water. Volume 3, page 243 (1931).

I Petroleum emulsions are of the water-in-oii The structural formula for oleic acid maybe "3 type, and comprise fine droplets of naturally written' as follows: occurring waters or brines, dispersed in a..more z. or less permanent state throughout the 11 which aa CH-(CH=)1COOH v constitutes the continuous phase'of the emulsion. Ordmary 15 characterized by the a They are obtained from producing wells and from that the unsaturated bond (ethylene linkage) 10 the bottoms of oil storage tanks,- and are comcurs between h ninth and tenth carbon mm refer ed to as when one considers the carboxyl carbon atomas sified oil", and bottom settnngs; the first one. When sulfuric acid or, more pref- The bje t of our invention is to, provide a erably, sulfuricacid monohydrate, reacts with novel, inexpensive and emcient process for olerc acid at relatively low temperatures, such as arating emulsions of the kind referred to ,into is formed a fatty acid sulfate by their component parts of oil and water or brine. w i a the unsaturated This a- Briefly described, our process consists in subanal 1s mdlcated by h following formula: iectini a petroleum emulsion of the water-'in-oil HSO4H ype, o the action of a treating agent or de- 20 mulsifying agent of a particular kind or comclHawl-hhm (onfl'coog a position hereinafter described, thereby causing If sulfonatian takes Place near the the emulsionto'break down and separate into s point f water, t a b e believed that its component parts of oil and water or brine, there formed a Sulfloniqi c as ShOWn by t 'when the emulsion is permitted to remain in a followmg formula;

quiescent state after. such treatment, or equiva- HSO8OH lent separatory procedure.

The treating agent or demulsifying agentus'ed pn'wnmg' (IHNOHQ'GQOH in our process consists of fatty sulfonic acids or (see Fats, Natural synthetic Myddleton & their salts or .esters, characterized by the fact a y, enn. 1924, page 57-.) c that the sulfonic acids are of the type corre- T manufacture of fatty sulfonlc acids,

' sponding to the general formula; tended-to be employed as catalysts in the hydrolytic splitting of fats, was originally disclosed in U. S. Patent 'No. 601,603, to Twitchell, dated as BS0801! March 29, 1239s. These materials, so produced in which R and R are aliphatic radicals or subaccording thediscloslll'e 9 said Twltchell D stituted aliphatic radicals, for instance, an alin a r ognized. as being saturated sulf'onic phatic radical having .a hydroxy' or carboxyl 'acids, because they have'no iodine value; do not group, and X is a hydroxyl radical or halogen decompose. on boiling with dilute hydrochloric 40 Such.sulfonic acids maybe derived from unsat- M and give slllfltes 011 fuSiOn with caustic Soda 40 urated fatty acids or fats. such as oleic acid, or caustic o Due to their sv' a ty olive oil, neatsfoot oil, linoleic acid, fatty acids 861d sulfates. Sometimes referred to 88 tty d ri d from fish ofl, and t 11ke Likewise, Cesteraor even as fatty acid esters, and whose such sulfonic acids may be derived fromricinoleic composition and Structure 15 Well wn. the e acid or castor'oil', u the sulfonating agent emwi ch tty sulfonic acids, are qu n y held ployed is in ample excess of the amount necesto be 0! the omposition and structure as indisary for sulfonation ofthe alcoholiform hydroxyl. cated by the above formula and reference to We are aware of the fact-that fatty sulfonic Myddleton and Barry. However, Twitchell, Jouracids are members of a class of materials known nal of the Society of Chemical Industry,'.Vo1ume as modified fatty acids, and that said, modified: 36, page 1'79 (1917), indicated that such a simple 50 j fatty acids are used extensively in the demulsiformula probably did not represent the actual .flcation of cut or emulsified oil. Also that sulfo facts, and that the material itself was an ester fatty acids or' salts or esters thereof have been acid type of body. as differentiated from the in extensive use fora long time for breakingcut, simpler formula previously described, and freli oil emulsions. Such sulfo acids included as their quently accepted. especially for purposes of com- 66 disclosed in U. s. Patent No.

2 parison, with fatty acid sulfates, or with sulfonic acids in which the sulfonic acid radical is not at- I tached to either the ninth or tenth carbon atom.

-- U. S. Patent No. 1,931,491, dated October 24,

5 1933, to Haussmanmdescribes'the manufacture of fatty sulfonic acids derived from unsaturated fattyacids at low temperature andunder certain peculiar conditions. Sulfonic-acids so obtained and until'recently unknown, have a composition which is in agreement with the formula proposed by Myddleton and Barry, in 1924, v. s., for fatty sulfonic acids produced at or near the boiling point of water, as first described by Twitchell. If oneproduces .sulfonic acids according to the method described in said recent U. S. Patent No. 1,931,491, and then purifies said sulfonic acids from .unsulfonated fatty material, fattysulfates, free sulfuric and hydrochloric acids-and the like in the conventional manner, such as the method of purifying fatty acid sulfates described in U. S.

Patent No. 1,894,759, dated January 1'], 1933, to

De Groote and Wirtel, then one obtains a relatively pure fatty sulfonic acid which is different in appearance and in chemical constants from the purified fatty sulfonic acid derived by action of -sulfuric acid on the fatty body at or near the boiling point of water. Careful investigation re- .vea'ls that fatty sulfonic acids produced in the "manner described in U. 8-. Patent No. 1,931,491,

previously referred to, conform in ultimate composition-and inproperties to the formula previously given by Myddleton and Barry for the older type offatty sulfonic acids made at the boiling point of water. sulfonic acids made near the boiling point of water confirms ester type of compound. Thus, one concludes that the earlier suggestion of Twitchell is correct, and that sulfonic acids of the type recently 1,931,491 are substanding" the suggestion of-Myddleton and Barry in 1924, because the product described by Myddleton and Barry is not a sulfonic acid of the type indicated bytheir proposed formula. Presumably Myddleton' and Barry intended this formula solely for purpose of comparison kind described in- U. 8. Patent No. 1,931,491 as true fatty sulfonic acids. we have found that these true sulfonic acids are very effective treating agents for' br'eaking' many oil field emulsions.

In some instances, emulsions may bebroken more readily by fatty acid esters of sulfuric acid or by some other type of sulfonic acid, for instance,-the older jlwitchell type of ester acid sulfonicj acid'or 1-,ese,ess

Further examination of fatty that such materials represent an.

'oas -cnon no'oo-oinn-dn-smom-nooo-oimrrr-somn stantially new compositions of matter, notwith-' with fatty acid 1 sulfates and not as an indication of ultimate com- '60 position.

We refer to these fatty-sulfonic acids of the .l flcation by action 'of these true sulfonic acids in the forms of acids, salts, or esters than by any other available reagent. The present invention contemplates the use of such true sulfonic acid bodies for breaking oil field emulsions, and is an improvement on prior processes employing demuisifying agents of the kind known or available before thedate of said Haussmann patent.

The manufacture of reagents, intendedv for use as the demulsifying agent of our process, is described completely in U. S. Patent No. 1,931,491, previously referred to. We prefer to prepare our reagent demulsifying agent in the following manner:

140 pounds of chlorsulfonic acid are added to 100 pounds of ethyl ether, while suitable cooling means are being applied so as to hold the temperature under 10 C. 282 pounds ofoleic acid are gradually added, and the temperature is then raised to about '20 C. During the reaction it is advisable to remove from the mixture any hydrogen chloride that may be formed. One suitable procedure is to pass a dry current of air, which has been saturated with ether, through the reaction mixture. Atthe end of 24 hours the sulfonation mass is poured into water, and the ether is eliminated by heating. A sulfonated oleic acid of the composition above referred to j and which is soluble in water and stable towards acids, is obtained; A washing process is employed to remove the excess of inorganic acid. The fatty product contained in the upper layer is neutralized with strong ammonia to the methyl orange indicator end point, so that the acid hythe sulfonic group'is completely redrogen of placed. Obviously, the'lower'waste' acid layer is withdrawn before neutralization. An equivalent amount of propyl ether may be employed instead of ethyl ether. The reaction apparently proceeds according to the following equations:

n Gilli earn-on Briefly described, the method 'of producing these process, comprises acting with an onium" comcentrated sulfuric acidon the unsaturated fatty true fatty'sulfonic acids intended to be used in our acid or fatty acid compound, underconditions so that the quantity of sulfonating agent is greater than one molecular proportion per molecular proportion of the fatty body, if the latter contains a hydroxyl group, as in the case of ricinoleic acid or castor oil. Onium compounds represent a group of organic compounds of the type RXH which are isologs of ammonium and contain the element X in its,highest positive valency. R is an aliphatic radical. Isologs, of course, represent any member of a series of compounds of similar structure, but having different atoms. However, as to the actual there is still question. Various structures, for. ex-' ample, have been ascribed to oxonium' compounds, a variety of may be considered as an addition acids (HCLHClOa) or its salts (SnCh).;-'1hey structural formation of onium'- compounds, I

onium compounds. They" compound or 1 double compound of an organic oxide with strong I nately combined. (as in b)'.

' I ammonium salts. 6

- pounds 'asmo're nearly example, by esteriflcation, or

.fonation can be performed were at first considered to have tetravalent oxygen. (as in a) and'later trivalent oxygen, co-ordi- They are analogous to trivalent bivalent 1 (co-orgasm) (addition(c)ompound) c 7 In studying the reaction between ethyl ether and chlorsulfonic acid, one may be helped to un- .derstand the reaction involved if one considers the type (a) formula suggested for the oxonium comrepresenting what actually takes place in these particular reactions, especially the'one involving ethyl ether and chlorsulfonic acid.

Thus, it has been found that true sulfonioacids can be produced from unsaturated fattyacids or their derivatives or mixtures thereof, in a simple manner by treating said fatty acids and the like with 'sulfonating agents stronger than sulfuric acid, which are reduced in their activity, as; for by formation of .a so-called onium compound, such as the oxoni um compound previously described. Thus, suleither with sulfonating agents such as chlorsulfonic or pyrosulfuric acid inthe presence of such compounds which are known to form therewith additive or other compounds of the type mentioned, or with esters of chlorsulfonic acid or substances furnishing the same, which substances are sometimes referred to as compounded sulfonating agents. 4

As examples of substances furnishing the aforefsaid additive or other products with the sulfonating agents may be mentioned; for example, diethyl sulfide, diethyl ether, acetic methyl ester, diethylene oxide, pyridine and the like. In some cases 1 the sulfonation is accompanied to some degree by another kind of substitution of the initial materials, for instance, the formation of a sulfonic acid containing chlorine, for example, when tetrahydrobenzene is treated with chlorsulfonic acid in the presence of ether. In such cases the halogen may, if desired, be easily removed, or replaced by other equivalent groups, by treatment with chemical agents such as water, alkalis, amines and the like. 4

These. true fatty 'sulfonic acids may be used.

as such for breaking petroleum emulsions, but it is preferable that they be used after neutralization with a basic material or'after este'r'ification with alcohol. Suitable bases for neutralization may be alkalinecompounds of sodium, potassium, or ammoniumsyIn some instances the calcium or magnesium salts formed by reaction with calcium -or' magnesium hydroxide or carbonate show marked water solubility and sometimes own oil solubility. In either event, they are suitable for use. Various aliphatic, aromatic, and'cyclic alcohols are suitable for esterification, including ethyl, methyl, propyl, etc; The esters thus formed may be water-soluble? or oil-soluble. In some instances, it may. be desirable to neutralize the hydrogen of the sulfonic radical, but not thehydrogen of the carboxyl radical. Amines maybe employed for neutralizing the true sulfonic acids, as in the case oftriethanolamine. The amine or ammonium salts are considered as being the equivalent of metallic salts. One acidic hydrogen may be replaced by one m, tal atom or by a radical, and

' group may be attached to either sulfonic acid body", as herein used,

some other substituent.

. In a general way, it-has been stated that the formula and structure of these true sulfonic acids is as follows: a,

' R-OHX rvnsolon in which R and R are aliphatic radicals, derived from unsaturated fatty acids, one of which contains a carboxyl group. The formula thus given is not intended to mean that only one single isomeric form may be used. In other words, the groups R and R may be reversed. The carboxyl R or R. The formula is intended to conform to the composition and general structure of the true sulfonic acid only. The formula might thus be rewritten:

to indicate that the aliphatic radical R in reality represents the aliphatic radical R" plus the conventional carboxyl group. As previously stated, the carboxyl group might be attached to the aliphatic radical constituting R. instead of R, as shown. Such a; true sulfonic acid is essentially a dibasic acid. Both the acidic hydrogen of the sulfonic acid radical and the acidic hydrogen of the carboxyl radical may be replaced by a metallic' atom, such as a sodium atom or an amine radical or analcohol radical, such as an ethyl radical, etc. Thus, the formula may be rewritten:

the salt, ester, or amine derivative thereof. Z

represents the acidic hydrogen equivalent.

It is not necessary that the true fatty sulfonic acids as such or in the form of salts and esters be separated from accompanying fatty material or small amounts of solvent, such as ether, which may remain in the finished product. The presence of amine residue-or radical small amounts of uncombined acid or 7 fatty acid esters of sulfuric acid are not objection- 'able.

combination with other recognized demulsifying agents, such as watersofteners, other modified fatty acids, salts of petroleum alkylated aromatic sulfonic acids, derivatives of polybasic' carboxy acids, and the like.

It is understood that the term true fatty should not be interpreted as referring only to the true sulfonic acids in their acidic fstate, but is intended to include the salts and describing these true fatty sulfonic acid bodies as containing an aliphatic radical, it is obvious,

of course,-that such radical is not limited to un substituted hydrocarbon radicals, but may include some other radical such as a radical as part of the substituted aliphatic radical."

In practising our process, demulsifying'agent of the may be brought in contact These materials may be employed alone or in' esters just as well. In

hydr w suli'onic acids,

a treating agent or kind above described with the emulsion to be treated in any of the numerous ways how em- -oil storage tank. In

- advisable to introduce the treating agent in to a producing well in such a mixed with water and oil way that it-will become that are emerging from the surrounding strata, before said water and oil "enter the barrel of the well pump or the tubing up through which said water and oil flow to the surface of the ground. After treatment, the emulsion is allowed to stand in a quiescent state, usually in a settling tank, and usually at a temperature. varying from atmospheric temperature to about 200 F. so as to permit the water or brine to separate from the oil,'it being preferable to keep the temperature low enough to prevent the volatilization of voluable constituents of the oil.

, the ratio of 1:500,

-pounded sulfonating agent obtained If desired, the treated emulsion maybe acted upon by one or more of the various kinds of apparatus now used in the operation of breaking petroleum emulsions, such as homogenizers, hay tanks, gun barrels, filters, centrifuges, or electrical dehydrators.

The amount of treating agent that may be required to break the emulsion may vary from approximately 1 part of treating agent to 500 parts of emulsion, up to 1 part of treating agent to 20,000 or even 30,000 parts of emulsion. The proportion depends on the type of emulsion being treated, and also upon the equipment being used,

and the temperature employed, In treating exceptionally refractory emulsions of the kind tank bottoms", and residual pit oils",

above referred to, may be required. In treating fresh known as the ratio of l:30,000, above referred to, may be sufficient to produce highly satisfactory results.

In general, we have found that for an average petroleum emulsion, a ratio of 1 part of treating agent to 10,000 parts found to produce commercially satisfactory results.

Having thus claim as new and Patent is: v -f q 1. 'A process for breaking petroleum emulsions of the water-in-oil type, jecting the emulsion to the action of a demulsifying agent produced by reaction between acomby reaction between chlorsulfonic acid and ethyl ether, and oleic acid at arelatively low temperature, followed by a conventional washing procedure with water, and'neutraliaation ofthe fatty material described our invention, what we desire to secure by Letters the bottom of an --of the water-in-oil type, which v emulsions,- i. e., emul sions that will yield readily to the action of ch'emical demulsifying agents,

. of the water-in-oil of emulsion will usually be which consists in sub-- with strong ammonia until the product is neutral to methyl orange indicator.

2. A- process for breaking of the water-in-oil type, which jecting the emulsion to tying agent produced by reaction between a compounded onium sulfonating agent derivedfrom a sulfonating agentstron'ge'r than concentrated sulfuric acid and an unsaturated fatty .body' at a relatively low temperature.

,3. 'A process for breaking petroleum emulsions of .the water-in-oil type, which jecting the emulsion to the action of ademulsi- -fying agent produced by reaction between'a compounded onium sulfonating agent derived from chlorsulfonic acid and an unsaturated fatty body at a relatively low tempera 4. A process for breaking of the water-in-oil type, which consists in subjecting the emulsion to the action of-a demulsifying agent produced by reaction'between a confpounded onium sulfonatln chlorsulfonic acid and an unsaturated fatty acid ata relatively low temperature.* A

5. A process for breaking petroleum emulsi of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulslconsists. in subvfying agent produced from chlorsulfonic acid by reaction between a compounded'onium s'ulfonating agent and oleicacid at arelatively low temperature.

6. A process for 'consists in subjecting the emulsion to theaction of a demul sifying agent produced by reaction between a compounded onium sulfdnating agent derived from chlorsulfonic acid and, ether, at. a relatively low temperature.

7. A process for breaking of the water-in-oil jecting theemulsion sifying agent in the form of reaction between a compounded onium sulfonating agent derived from chlorsulfonic acid and ether, and oleic acid at a relatively low-temperature.

8. A process produced by reaction between 'a con' pounded onium sulfonating agent derived from chlorsulfonic acid and ether, and oleic acid at a relatively low temperature.

mvm an encore: BERN'HARD-KEIBER.

the action of a dernulsi-v to theaction' of a demul-.

a salt, produced by and oleic acid at a rela-' petroleum emulsions consi'sts-insuhpetroleum emulsions I agent derived from breaking petroleum emulsions for breaking petroleum emulsions typ 'which consists in subto the action of'a demul- 

